EP0008216A1 - Improvements in unsaturated polyester resins and methods of making them - Google Patents
Improvements in unsaturated polyester resins and methods of making them Download PDFInfo
- Publication number
- EP0008216A1 EP0008216A1 EP79301587A EP79301587A EP0008216A1 EP 0008216 A1 EP0008216 A1 EP 0008216A1 EP 79301587 A EP79301587 A EP 79301587A EP 79301587 A EP79301587 A EP 79301587A EP 0008216 A1 EP0008216 A1 EP 0008216A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- unsaturated polyester
- polyester resin
- resin composition
- composition according
- hydrocarbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 14
- 230000008020 evaporation Effects 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 230000005764 inhibitory process Effects 0.000 claims abstract description 8
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 27
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229930195734 saturated hydrocarbon Natural products 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- -1 vinyl compound Chemical class 0.000 abstract description 5
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 abstract description 2
- 239000012188 paraffin wax Substances 0.000 description 11
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 3
- RJWUMFHQJJBBOD-UHFFFAOYSA-N 2-methylheptadecane Chemical compound CCCCCCCCCCCCCCCC(C)C RJWUMFHQJJBBOD-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- QJJDJWUCRAPCOL-UHFFFAOYSA-N 1-ethenoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOC=C QJJDJWUCRAPCOL-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000549173 Celastrus scandens Species 0.000 description 1
- 241000764064 Mycobacterium phage Glass Species 0.000 description 1
- GWFGDXZQZYMSMJ-UHFFFAOYSA-N Octadecansaeure-heptadecylester Natural products CCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC GWFGDXZQZYMSMJ-UHFFFAOYSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003435 aroyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
- C08F299/0478—Copolymers from unsaturated polyesters and low molecular monomers characterised by the monomers used
Definitions
- Particularly preferred compounds are those in which R is a straight-chain unsubstituted hydrocarbon, especially with 12 or 18 carbon atoms, namely lauryl or stearyl and those where n is 1, X is and Y is methyl, namely lauryl and stearyl methacrylates.
- Example 6 The same composition as used in Example 6 was made except that the vinyl decanoate was replaced by 20g lauryl vinyl ether. The styrene evaporation rate after 10 minutes was 12g/m2 and after 30 minutes 29g/m 2 . No loss of adhesion between successive laminations was noted.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
To allow inhibition of styrene evaporation from an unsaturated polyester resin during curing, there is present in the resin a small amount (0.1 to 5% by weight) of a long- chain vinyl compound of the formulawherein R is a straight or branched-chain substituted or unsubstituted aliphatic C<sub>6</sub>-C<sub>24</sub> hydrocarbon, Y = H or CH<sub>3</sub>, n = zero or 1, X - -O-C- or-O-. OPreferred such compounds are lauryl and stearyl methacrylate.The resins are made by admixture of the selected compound(s) with the conventional other components of the resin.
Description
- The invention relates to unsaturated polyester resins, to methods of making them, and in particular to the inhibition of the evaporation of styrene monomer therefrom.
- It has been known for many years that the inclusion of small quantities of paraffin wax in polyester resins prevents air inhibition of the open surface of mouldings on cure (B.P.713,332). The wax works by migration to the open surface forming a thin layer which prevents air from interfering with the surface cure. The quantity needed depends on the melting point of the wax used, commonly a paraffin, although other waxy materials have been claimed, e.g. stearyl stearate (B.P.850,762). In· practice about 100 ppm. of a paraffin wax mp 52-540C has been employed.
- More recently a need has arisen on environmental grounds to reduce the evaporation of styrene monomer from the surface of a laminate in the interval between lay-up and cure. This can be achieved by the incorporation of higher levels of paraffin wax, and the effect of different levels of wax on the styrene loss is progressively greater as the levels of paraffin wax increase up to about 800 ppm. for most types of resin, although some types will require even more wax.
- However, at the higher levels of wax required to substantially reduce styrene evaporation several drawbacks have been noted:-
- (i) the wax can separate from the liquid resin when it is stored at low temperatures,
- (ii) the layer of wax can interfere with the adhesion between one layer of laminate and the next, especially where there is a delay between lay-up and cure.
- Several methods of overcoming these disadvantages have been proposed i.e. the incorporation of small quantities of a straight chain hydrocarbon, e.g. n-octane, or the use of surfactant such as a polyoxyethylene sorbitan fatty acid ester (German Offenlegungsschrift 2554930).
- Neither of these methods has been particularly successful. For example 2% n-octane lowers the heat deflection temperature of the cured resin and imparts a milky appearance to the laminate.
- The present invention faces the task of allowing efficient inhibition of styrene evaporation by adding the larger quantities of paraffin wax or other ingredient which are needed in comparison to the quantities which would have been needed merely for the prevention of air inhibition (air inhibition is an effect of the atmosphere on the surface layer of the laminate so that it does not cure properly), without however, involving the penalty of loss of adhesion or spoiled appearance. Furthermore, the present invention will permit the preservation of the desired heat deflection temperature in the cured resin.
- In the invention therefore we admix with the conventional components of an unsaturated polyester resin composition (which conventionally consists of a prepolymer plus styrene as a vehicle and cross-linking agent and an accelerator, to which is then added a catalyst when curing is desired), an unsaturated compound which is theoretically capable of taking part in the cross-linking reaction.
- These compounds are of the formula
R = a straight- or branched-chain substituted or unsubstituted, aliphatic C6-24 hydrocarbon.
n = zero or 1 and
X =
and includes both vinyl and acrylic esters, i.e. esters where
- There has been a disclosure in U.K. Patent 862583 of the modification of an alkyd resin by the incorporation into it of styrene and a methacrylate, including 2-ethylhexyl methacrylate and n-octyl methacrylate. Of course, this is quite different from a polyester resin composition of the type we are concerned with here since . in that case both modifiers are incorporated into the monomer component and are not active in the curing stage, which occurs through the unsaturated oil components of the alkyd. The problem of styrene evaporation does not, of course, arise in that composition at all since the styrene is chemically bound into one ingredient of the total composition.
- The invention includes the use of those compounds where, by the nature of the alcohols containing the group R from which esters or ethers are prepared, the groups R have a mixture of chain lengths, and although normally only one such compound will be used in a composition, there is no exclusion of the use of a plurality of such compounds.
- Examples of branched- chain hydrocarbons R are 2-ethyl-hexyl, tridecane and iso-octadecane and examples of substituents are alkyl, aryl, carboxyalkyl, hydroxyl, alkoxyl, and aroyl groups and halogen atoms (though iodine and bromine would not be desirable substituents - and nor would an amino group).
- The styrene used as a vehicle will, in a commercial situation, be styrene itself, but in principle, substituted styrenes may be used.
- A preferred hydrocarbon of the group R is a C6-18 or even C6-24 hydrocarbon, C8-22, especially C8-18, hydrocarbons being more preferred. The hydrocarbon should be saturated.
- Particularly preferred compounds are those in which R is a straight-chain unsubstituted hydrocarbon, especially with 12 or 18 carbon atoms, namely lauryl or stearyl and those where
n is 1,
X is
Y is methyl,
namely lauryl and stearyl methacrylates. - Typical examples of suitable compounds are n-octadecene, lauryl methacrylate, vinyl stearate and vinyl stearyl ether.
- Amounts of 0.1-5% by weight of the said compound can be used, but the preferred range is 0.5-2.5%.
- These amounts of component allow the use of quantities of paraffin wax and/or similar ingredients much larger than those which would have been needed merely for the prevention of air inhibition and yet such large amounts can be incorporated in the composition without any of the previously mentioned disadvantages associated with these known ingredients.
- Preferred embodiments of the invention will now be described in more detail with reference to the following Examples, which illustrate the excellence of such embodiments.
- To lkg of CRYSTIC® 406PA (an orthophthalic acid based pre-accelerated general purpose polyester) there was added 0.75g paraffin wax, m.p. 52-54°C, and 20g lauryl methacrylate.
- 500kg of this mixture was mixed with lOg methyl ethyl ketone peroxide (Butanox M50) and this was used to make a glass fibre laminate 0.5 sq.m. in area using one layer of 450g/sq.m. glass matt. After 24 hours the other half of the resin was catalysed and a further layer of glass matt laminated onto the first.
- After a further period of 24 hours a laminate of good clarity was tested for interlaminar adhesion and it was very difficult to separate the two layers.
- The heat deflection of a cast of the resin mix (when determined according to B.S.2782 Method 121A) was 62°C.
- The procedure of Example 1 was followed except that the lauryl methacrylate was omitted. The final laminate had poor interlaminar adhesion and could be easily peeled apart.
- The heat deflection temperature of a cast of the resin mix was 62°C.
- The procedure of Example 1 was followed, except that thelauryl methacrylate was replaced by an equal weight of n-octane. The final laminate had a milky appearance, and whilst the interlaminar adhesion was better than the laminate of Example 2 it was inferior to that of Example 1.
- The heat deflection temperature of a cast of the resin mix was 54°C, i.e. it had been depressed by the n-octane present.
- To lkg. of Crystic® 406 PA (an orthophthalic acid- based pre-accelerated general purpose polyester) there was added 1.00g paraffin wax, m.p. 52-54°C, and 10.0g stearyl methacrylate. A laminate made up as described in Example 1 had a styrene evaporation rate. of 3g/m2 in 10 minutes and 4g/m2 in 30 minutes. Excellent adhesion between successive laminations was obtained.
- To lkg. of Crystic® 491 PA (an isophthalic acid based resin) there was added 1.0g paraffin wax, m.p. 52-54°C, and 1.25g stearyl methacrylate. Laminates from this formulation had a styrene evaporation rate of 7g/m2 in 10 minutes and 9g/m2 in 30 minutes. Excellent interlaminar adhesion was obtained under all conditions.
- To lkg. of Crystic® 406 PA there was added 0.75g paraffin wax, m.p. 52-54°C, and 20g vinyl decanoate. A laminate made up as described in Example 1 had a styrene evaporation rate of 1g/m2 in 10 minutes and 2g/m2 in 30 minutes. Excellent adhesion between successive laminations was obtained.
- The same composition as used in Example 6 was made except that the vinyl decanoate was replaced by 20g dec- l-ene. The styrene evaporation was 8g/m2 and after 30 minutes 12g/m2. Again excellent adhesion between successive laminations was obtained.
- The same composition as used in Example 6 was made except that the vinyl decanoate was replaced by 20g lauryl vinyl ether. The styrene evaporation rate after 10 minutes was 12g/m2 and after 30 minutes 29g/m2. No loss of adhesion between successive laminations was noted.
- The same composition as Example 6 was made except that the vinyl decanoate was replaced by 7-5g. C22-C24 alkyl methacrylate. The styrene evaporation rate was 2g/m2 after 10 minutes and 3g/m2 after 30 minutes. Very good interlaminar adhesion was obtained.
Claims (10)
1. An unsaturated polyester resin composition containing styrene as an agent for cross-linking during curing characterized in that there is present to allow inhibition of styrene evaporation, a compound which is theoretically capable of taking part in the cross-linking reaction and is of the formula
wherein Y = H or CH3
R = a straight-or branched-chain substituted or unsubstituted aliphatic C6- C24 hydrocarbon,
n = zero or 1 and
x = 
or -0-
R = a straight-or branched-chain substituted or unsubstituted aliphatic C6- C24 hydrocarbon,
n = zero or 1 and
x =
2. An unsaturated polyester resin composition according to claim 1, wherein R is a C6- C18 said hydrocarbon.
3. An unsaturated polyester resin composition according to claim 2, wherein R is a C8- C16 said hydrocarbon.
4. An unsaturated polyester resin composition according to claim 1, wherein R is a C18- C24 said hydrocarbon.
5. An unsaturated polyester resin composition according to claim 4, wherein R is a C18- C22 said hydrocarbon.
6. An unsaturated polyester resin composition according to any one of the preceding claims wherein X is
n is 1 and R is a C8, C12 or C18 straight-chain unsubstituted saturated hydrocarbon.
7. An unsaturated polyester resin composition according to claim 6, wherein the compound is lauryl methacrylate.
8. An unsaturated polyester resin composition according to claim 6, wherein the compound is stearyl methacrylate.
9. An unsaturated polyester resin composition according to any one of the preceding claims, wherein the compound is present in an amount of 0.1 to 5 % by weight of the composition.
10. An unsaturated polyester resin composition according to claim 9, wherein the compound is present in an amount of 0. 5 to 2.5 % by weight of the composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT79301587T ATE1711T1 (en) | 1978-08-08 | 1979-08-06 | IMPROVEMENTS IN UNSATURATED POLYESTER RESINS AND PROCESSES FOR THEIR MANUFACTURE. |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB3255478 | 1978-08-08 | ||
| GB7832554 | 1978-08-08 | ||
| GB7903499 | 1979-02-01 | ||
| GB7903499 | 1979-02-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0008216A1 true EP0008216A1 (en) | 1980-02-20 |
| EP0008216B1 EP0008216B1 (en) | 1982-10-27 |
Family
ID=26268474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP79301587A Expired EP0008216B1 (en) | 1978-08-08 | 1979-08-06 | Improvements in unsaturated polyester resins and methods of making them |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4285845A (en) |
| EP (1) | EP0008216B1 (en) |
| AU (1) | AU523371B2 (en) |
| BR (1) | BR7904997A (en) |
| CA (1) | CA1134530A (en) |
| DE (1) | DE2963937D1 (en) |
| ES (1) | ES483178A1 (en) |
| FI (1) | FI66013C (en) |
| NO (1) | NO152756C (en) |
| NZ (1) | NZ191201A (en) |
| PT (1) | PT70031A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4347170A (en) * | 1979-10-12 | 1982-08-31 | Internationale Octrooi Maatschappij "Octropa" B.V. | Unsaturated polyester compositions and their use |
| EP0442953A1 (en) * | 1988-11-09 | 1991-08-28 | BRIGHT, Elvin Merrill | Optical plastics and methods for making the same |
| US5378743A (en) * | 1989-11-08 | 1995-01-03 | The Dow Chemical Company | Stable low styrene emission vinyl ester and unsaturated polyester resin composition |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4336169A (en) * | 1979-12-21 | 1982-06-22 | Scott Bader Company Limited | Unsaturated polyester resins |
| US4387171A (en) * | 1981-04-23 | 1983-06-07 | Scott Baker Company Limited | Unsaturated polyester resins |
| CA1211242A (en) * | 1984-02-10 | 1986-09-09 | Peter L. Mena | Polyester laminating compositions with improved interlaminar adhesion |
| DE3504272A1 (en) * | 1985-02-08 | 1986-08-14 | Battelle-Institut E.V., 6000 Frankfurt | METHOD AND DEVICE FOR BIRD COMBAT |
| GB8626080D0 (en) * | 1986-10-31 | 1986-12-03 | Unilever Plc | Detergent composition |
| US5177127A (en) * | 1991-01-28 | 1993-01-05 | Reichhold Chemicals, Inc. | Molded composite polyester articles having improved thermal shock resistance |
| DE4314866A1 (en) * | 1993-05-05 | 1994-11-10 | Bayer Ag | Radically curable lacquer composition and its use as furniture lacquer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB710513A (en) * | 1950-10-19 | 1954-06-16 | Union Carbide & Carbon Corp | Polyester terpolymers |
| US3042651A (en) * | 1959-06-19 | 1962-07-03 | Sherwin Williams Co | Polymerizable composition containing unsaturated polyester, an acrylic ester, a monovinyl benzene and a vinyl ester of an alkyl carboxylic acid |
| FR2084793A5 (en) * | 1970-03-18 | 1971-12-17 | Berger Jenson & Nicholson Ltd | |
| US3721722A (en) * | 1970-07-16 | 1973-03-20 | Koppers Co Inc | Thickenable unsaturated polyester resin system |
| FR2228095A1 (en) * | 1973-05-03 | 1974-11-29 | Cauwenberghe Helic Van | Polyester varnish compsn contg acrylate plasticiser - for application by contact UV process |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3188363A (en) * | 1961-09-13 | 1965-06-08 | Us Rubber Co | Inhibitors of premature gelation in polyester resins |
| US3507933A (en) * | 1967-03-03 | 1970-04-21 | Dow Chemical Co | Self-extinguishing polyester compositions of 2,2-bis(bromomethyl)-1,3-propanediol and method of making the same |
| US3983185A (en) * | 1973-07-30 | 1976-09-28 | Hooker Chemicals & Plastics Corporation | Halogen containing polyester resins having improved smoke-resistance |
| US4041008A (en) * | 1975-05-12 | 1977-08-09 | Ppg Industries, Inc. | Low smoke density fire-retardant resins |
-
1979
- 1979-07-31 AU AU49408/79A patent/AU523371B2/en not_active Expired
- 1979-08-03 BR BR7904997A patent/BR7904997A/en not_active IP Right Cessation
- 1979-08-03 US US06/063,134 patent/US4285845A/en not_active Expired - Lifetime
- 1979-08-03 NZ NZ191201A patent/NZ191201A/en unknown
- 1979-08-06 PT PT70031A patent/PT70031A/en unknown
- 1979-08-06 DE DE7979301587T patent/DE2963937D1/en not_active Expired
- 1979-08-06 EP EP79301587A patent/EP0008216B1/en not_active Expired
- 1979-08-07 FI FI792442A patent/FI66013C/en not_active IP Right Cessation
- 1979-08-07 ES ES483178A patent/ES483178A1/en not_active Expired
- 1979-08-07 NO NO792582A patent/NO152756C/en unknown
- 1979-08-08 CA CA000333379A patent/CA1134530A/en not_active Expired
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB710513A (en) * | 1950-10-19 | 1954-06-16 | Union Carbide & Carbon Corp | Polyester terpolymers |
| US3042651A (en) * | 1959-06-19 | 1962-07-03 | Sherwin Williams Co | Polymerizable composition containing unsaturated polyester, an acrylic ester, a monovinyl benzene and a vinyl ester of an alkyl carboxylic acid |
| FR2084793A5 (en) * | 1970-03-18 | 1971-12-17 | Berger Jenson & Nicholson Ltd | |
| US3721722A (en) * | 1970-07-16 | 1973-03-20 | Koppers Co Inc | Thickenable unsaturated polyester resin system |
| FR2228095A1 (en) * | 1973-05-03 | 1974-11-29 | Cauwenberghe Helic Van | Polyester varnish compsn contg acrylate plasticiser - for application by contact UV process |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4347170A (en) * | 1979-10-12 | 1982-08-31 | Internationale Octrooi Maatschappij "Octropa" B.V. | Unsaturated polyester compositions and their use |
| EP0442953A1 (en) * | 1988-11-09 | 1991-08-28 | BRIGHT, Elvin Merrill | Optical plastics and methods for making the same |
| EP0442953A4 (en) * | 1988-11-09 | 1991-10-30 | Elvin Merrill Bright | Optical plastics and methods for making the same |
| US5319007A (en) * | 1988-11-09 | 1994-06-07 | Bright Elvin M | Optical plastics and methods for making the same |
| US5378743A (en) * | 1989-11-08 | 1995-01-03 | The Dow Chemical Company | Stable low styrene emission vinyl ester and unsaturated polyester resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| AU523371B2 (en) | 1982-07-22 |
| FI792442A (en) | 1980-02-09 |
| FI66013B (en) | 1984-04-30 |
| EP0008216B1 (en) | 1982-10-27 |
| FI66013C (en) | 1984-08-10 |
| NO152756B (en) | 1985-08-05 |
| NZ191201A (en) | 1980-12-19 |
| NO792582L (en) | 1980-02-11 |
| AU4940879A (en) | 1980-02-14 |
| US4285845A (en) | 1981-08-25 |
| PT70031A (en) | 1979-09-01 |
| NO152756C (en) | 1985-11-13 |
| CA1134530A (en) | 1982-10-26 |
| BR7904997A (en) | 1980-04-29 |
| ES483178A1 (en) | 1980-09-01 |
| DE2963937D1 (en) | 1982-12-02 |
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